Process for refining hydrocarbons



' Aprile, 1929.

J. C. BLACK E' AL PROCESS FOR lREFINING HYDROCARBONS Filed Ilarch 2, v1923 n (l @5g/mfom. w W( f. l Y QL ATTORNEKM Patented Apr. 16, 1929.

UNITED sfr-A JQHN C. BLACK, 0F DESTBEHXAN, LOUISIANA, TAKES W. WEIB, O FILLMORE,

\ CALIFORNIA.

rnocnss y:son REFINING H Ynnocnnnous.

Application med :kann 2, 192s. serial No. 622,386.'

This invention relates to the process of reining hydrocarbons and more particularly to boiling-points, etc., demanded by the trade,v

directly from the crude oil with one distillation.

Ve accomplish this object by distilling the oil and passing the distilled vapors to a dephlegmating tower or similar apparatus and we control the temperature of such tower by withdrawing from near the bottom such condensates as are formed therein, cool the same and returnthe cooled condensate to the tower where they are brought into contact with the. distilled vapors, thus washing, scrubbing and condensing part of the vapors, allowing other vapors to pass out of the tower or similar apparatus through a .cooling apparatus Where they are condensed.

We may use a succession of stills and towers if desirable, maintaining each of the towers at such temperatures as may be desired by regulatingthe speed of the pumps which circulate thelliqueed portion of the oil through the towers and by means of the circulating liquid we may condense and remove from the mixed vapors the higher boil-` ing point oils and allow the lower boiling point'oils to pass on as a residual vapor, condense the same and mix them as desired to produce a finished gasoline directly from the oil, eliminating the usual steam dis tilling process. t

These results may be obtained by an apparatus shown and described in the single figure of drawings accompanying this application in which: i

1 represents a still in which for example oil is charged through a charging line 2 from a source of supply not shown, which is heated y by heatapplied through fire box 3 sufficiently to cause vapors to rise and pass off through dome 4, vapor line 5, into tower 6, up through a battling medium which for convenience is shown on the drawing as baffles 7, out through vapor line 8, through condenser coil 9 where the vapors are condensed, coil 9 being situated in cooler box 10 and submerged in cold water supplied.- through line 11 from a source ofy supply not shown.' The condensate from coil 9 passes through `look box 12 and rundown line 13 mto receiving tank 14.

A still o f this type can be run separately, charged with oil from a source of supply 1n single batches, or semi-continuously, allow` ing the residuum to accumulate in still untilfully charged as the vapors are driven off, in

either of which cases when run is complete residuum'ls withdrawn from still l through dump line 16, pipe 42, valve and line 43 to ceoler and receiving tank not shown; or contxnuously from a source of supply, allowingA the residuum from which the 'vapors are being continuously distilled off as above descrlbed to overflow fromstill 1 through overflow line 15 into still 1--A, where the process of dlstillation is continued and more vapors are continuously distilled olf through dome l-A, vapor line 5--A, ytower G-A up through a balling medium which for con` venlence 1s Shown on drawirlg as ,bailes 7-A,

out through vapor line VS--I-A,`r through coil 9- A where vapors are condensed, coil 9-A bemg situated in cooler box IO-A and submerged in cold water supplied through line ll--A from a source of supply not shown. The condensate from coil 9-A passes through lookvbox 1Q-A and rundown line 13-A into recelvmg tank 14-A. The residuum from which the vapor is being continuously dis-y not shown.

While only two stills are shown anddescribed in this drawing and specifications 1t 1s to be understood that any number o stills can be similarly arranged in series and run continuously, taking off any quantity of vapors in such fractions as desired.

While such arrangements are not shown, stills may be equipped or not as desired with steam pipes for steam distillation. It is also to be understood that the stills may be heated by fire as described, or by steam or any other means for heating or means to induce vaporization.

It 1s also to be understood that the oil may be distllled for any purposeand the use of this method is applicable and beneficial wherever 1t 1s necessary or desirable to yuse dephlegmating towers or refiux condensers in any form, and an object of the invention is toy control the temperature of same when applied to and used in connection with dephlegn'iating towers and fractionating towers already in general use and common practice indestructive distillation or cracking stills, as well as in the production of wax distillate, where the crystalline structure is formed by a certain desired amount'ot destructive distillation, generally known as cracking, by refluxing the condensate from a tower back to the still from which it came.

1t is further to be understood that the above applies to steam stills, pressure still or vacuum stills, or a vapor-ization chamber in connection with a. pip(` still, or any other type of still, whether it be vacuum or pressure, wheie the reflux condensates from the tower may be returned or directed to a Zone where it is subjected to a Jfurther distillation treatment.

It is to be understood that this method is for the purpose of controlling the temperature of any dephlegmating tower, fractionitizg tower or condensing apparatus of any For the purpose of describing and giving a clear understandingr of the operation of the method which comprises our new'and useful discovery, we have given the above outline of a VI'generally accepted and well known method of distillation, and the method of our process as particularly applied to same is described below. It is to be understood, however, that this description is to illustrate and describe' the method employed and is not necessarily confined thereto. We will therefore consider that continuous distillation as heretofore described is in progress and that mixed vapors in accordance' with the'general and well known practice are coming'ol' and passing through. the apparatus as described.

The oil in still 1' is heated to a temperature of approximately 450 F. The vapors passing off through the tower and condensing apparatus are condensed and pass through look box 12 at a gravity of about 52 Baume. At the same time the oil in still 1A will be 5U`le`ated to a temperature of about 520 F., and

the vapors passing off through the tower and condensing apparatus are condensed andv pass through look box 12-A `at a gravity of about 46 Baume. VThis is in accordance with the general and well known practice. when' blended and mixed in the proportions as distilled make what is known in the art as crude naphtha, and in order to make commercial gasoline that is water white and to 'meet the specifications as to boiling points,

etc., demanded by the trade it is necessary to A redistill this stockin order to -properly fractionate and separate the lighter fractions fromv the heavier fractions which constitute The stocks being thus produced:

the crude naphtha which is the result of the total condensed mixed vapors distilled from thetwo stills as described.

By the method of fractionating which we employ we are enabled to eliminate this redistillation and make a merchantable com-- mercial gasoline of the specifications as to boiling points, etc., demanded by the trade direct from the oil with one distillation,

l which is accomplished as follows:

During `distillation vapors passing from still 1 through dome 4 and vapor line 5 into' tower 6 and upward through battles 7 are naturally cooled by expansion therein and contact with the baiHes while passing through the tower, and a certain amount of condensation takes place within the tower, which condensate collects upon the baffles and retluxes or flows backward to the bottom of the tower 6, filling outlet pipe 17 running by gravity through cooling Apipe 18 situated in cooler jacket 19 filled with cold water through inlet pipe 20 from a source of supply not shown. This cooler jacket if occasion requires maybe used as a heating jacket instead of a cooler by the admission of steam through pipe 21 by steam valve and line 24 from. a source `of steam supply not shown. Pump 23 dis charges this condensate through valve 34 and line 25 into the upper portion of tower 6, and it flows by gravity down over baiiies 7, coming into intimate contact with the mixed vapors passing upward through the tower and baliles, falling to the bottom of the tower, from whence it is circulated continuously through outlet pipe 17, cooling pipe 18, pipe 22 and valve 38, pipe 39 and valve 40, with pump- 23, valves 28 and 41 being closed. It will be obvious that the quantity of cooled condensate entering tower 6, regulated by the speed of the pump, will positively control the temperature of the vapors passing upward through the tower to any degree detower by the like circulating condensates and mixed therewith How to the bottom of tower G, and the excess amount accumulated or bc approximately 60 Beaum.

extracted by the like circulating medium not used and contained in the circulating system same quantity of distillate and the' excess l.

condensate will overflow and escape through any opening provided.

The residual vapors after having lbeen scrubbed as described pass upward from tower 6 through vapor line 8 into condenser coil 9 and are condensed. '.Fhecondensate flows from coil 9 through look box 12 and through rundown line 13 into receiving tank 14. Samples are taken from the stream of condensate passing through lookbo'x 12 at regular intervals, and the speed of pump 23 is so regulated by steam valve 24 that the gravity of the distillate flowing through look box 12 will be 60 Beaum, or any desired gravity for a finished product. The gravity of this stream can be and is absolutely controlled by the speed of the pump, which regulates the quantity of cooled condensate being circulated through the tower 6, which fractionally separatesA from the mixed oil vapors coming from still `1 while passing through tower 6 the heavy fractions having substantially the same composition as the circulating hydrocarbons being circulated' and returns or refluxes all of the excess separated and. condensed like hydrocarbons not used and contained in the circulating system to still 1, thereby control-- ling the gravity of the distillate flowingy through look box 12, which is the condensed residual vapors or light fractions of the mixed vapors from which the heavy fractions have been separated as described. The still is maintained at approximately the same temperature, viz, 450 F.

As previously described, it will be noted that the gravity of the stream before startingl to circulatethe condensate through the tower was 52- leaum in look box l12, whereas after circulating the gravity of this condensate will AThe gravity of the distillate can be positively regulated within the reasonable limits of the natural distillate content of the oil under distillation.

The residuum overflowing from still 1 through overflow pipe 15 into still l-A is heated to and maintained at a temperature of approximately 520 F., distilling oil' the vapors through dome fil-A, vapor line 5-'-A, into -tower 6-A, passing upward through baflles 7=A., out through vapor line 8A to condenser coil 9-A, where the va ors are condensed, coil 9-A being situated 1n cooler box 10'A submerged in waterfrom pipe 11-A from a source of supply not shown. The condensate from condenser coil 9-A from this still passes through look box `12-A, pipe 13--A to receiving tank 14-A. The gravlty of the condensate passing throu h'look box 12-A will be approximately 46 eaum.

Vith still l-A `running in a continuous battery with still 1 as above described, circulating equipment supplied and controlled by pump 23-A is mampulated'in a like manner as described in the manipulation of pump 23,

so as to control the gravity of distillate and raise it from 46 to 56 Beaum in like manner as inthe manipulation of pump 23 and apparatus as previously described in connection with still 1.4 Inasmuch as the manipulationand operation of' the control of the gravity of the distillate produced from still l--A by the pump 25E-A and the fractionating apparatus therewith connected is th same as described in connection with still 1; the. details of' this operation and manipulation are omitted for brevity.

The distillate thus produced with the aid of the fraetionating apparatus as described, when blended in the proportions as produced, makes a commercial water white merchantable gasoline of the specifications as to boiling points, etc., as demanded by the trade. This gasoline can be made to any desired specifications as to boiling points, gravity, etc., within the reasonable limits of the gasoline content of the oil under distillation by manipulation of the circulating distillate within the appa-- ratus.

vIt will be noted from the above that by this method we have produced a finished gasoline directly from the oil, eliminating the` llt) 30/30-A.' In this manner the mixed vapors coming from the stills can be fractionated or separated into= two' component parts. The properties of thesetwo component parts may Vbe varied to any 'degree Withinl the reasonable limits of the vapors.

It is further to be understood that by the addition of more towers to each still, fully natural content of the mixed equipped with. pump and circulating apparatus, arranged in series in the vapor lines 5 and 8, that the mixed vapors 4may be frac! tionated into any reasonable number of fractionsconsistent with'the total content" of the mixed vapors under distillation.

' It is further to'be understood that the excess condensate not contained and used in the circulating apparatus may be disposed of in various ways; for example, it ma be refiuxedor allowed to fiow by gravity from tower 6 to still 1-A by closing valves 28, 38 and 3l on reflux pipe 26V and "opening valve 27 on reiiux pipe 267 and Valves 32/32-A on cross-over reflux line 33, and opening valve 31 A on refluxlinc 26 A.

1t is to be understood that this operation maybe reversed as regards still l--A and its apparatus and still l and its apparatus; furthermore, if the lines of the apparatus as delineated on the drawing are followed it will be noted that the excess condensate not contained and used in the circulating apparatus may be disposed of in various ways as described hereafter: The excess condensate may be allowed to flow.back againv by gravity from the bottom of tower 6 to the still l from which it was received in vapor phase, this refluxing being accomplished by flowing through the line 2G', Valves 27 and 31 being open and valve 32 in branch line 33 being closed. In the same way as above the excess condensate of tower 6--A may be allowed to flow back to still 1-A.

The excess condensatemay be allowedto flow from tower 6 to still l-A where a higher temperature is maintained than in still l, this' refluxing occurring through line 26, branch line 33 and line 26-A, valves 27, 32, 32-A and 3l-'A being open and valve 31 'being closed, while. the reflux of excess condensate of tower (S-A may be allowed to How also The excess condensate of tower ..6 may be allowed to flow directly to a storage tank I3() through line 17, .18 and 29, valve28 being open and valve 27 in line 26 being closed. In the same way the excess condensateof tower G-A may be run down to storage tank 30-A.

It is further understood that the condensates from towers 6 and (i-A may be directed or discharged from pumps l23 andv 23-A from one part of the apparat-us to any other part of the apparatus of the Various stills and units thereof. This may be seen by following the lines as delineated in the drawing of the apparatus. It is to be understood, for example, that 'by closing valve 34 on line 25 and opening valves 35 and 85-A on cross-over line 36, pump 23 may discharge condensate from bottom of tower 6 through through the towers 6 and (-A in lieu of the condensate from said towers as heretofore described. rlhe residual oil, for example, will be used in the following described man# ner:

Suction will be taken from stills 1 and l-A through dump lines 16/l6-A, pipe 42/42-A and cooler pipes 37/37-A with pumps 23/23-A, discharging through lines 25/25 (V6- A, where the cooled'residuum flows by gravity ldown over bales 7/7-A, coming into intimate contactfwith the mixed vapors passing upward through the tower and bafiles, to the bottom of the tower, from whence itis passed back through valves 27/27-A, lilies 26/26-A and valves lf/l-A, valves 32/32-A being closed, to the still from which it came, mixed with the resultant eondensatefrom the towers, valves 28/28-'A and 38/38-A being closed.

We claim:

1. The process of fractionally separating mixed hydrocarbons having different boiling points' which consists in vaporizing the hydrocarbons and passing the vapors to the lower part of afractionating tower to condense the higher boiling point fractions as the vapors rise in the tower, withdrawing from an outlet at the bottom of the fractionating tower some of the liquid hydrocarbons condensed ther in and circulating the condensates back to the upper part of the tower and allowing them to flow back down through the tower, thus bringing them into A to the upper portion of towers intimate contact with the mixed vapors passl )ing up through said tower and liquefying and separating from the mixed vapors as they pass up through the tower, the fractions having substantially the same composition as the' circulated"hydrocarbons, and refluxing the resultant excess separated and condensed hydrocarbons not used in circulation back to the still from which the `mixed oil vapors were obtained. .f

2. The process of fractionally separating mixed hydrocarbons having different boiling point-s which consists in vaporizing the hydrocarbons and passing the vapors to the lower part of a fractionating tower to con.

dense the higher boiling point fractions as thev vapors rise in the tower, withdrawing iso from an outlet at the bottom of the fractionatin tower some of the liquid hydrocarbons con ensed therein and circulating them back to the upper art of the tower and allowing them to flow ack down through the tower,

thus bringing them into intimate contact withy the mixed vapors passing up through said tower and liquefying and separatin `from the mixed vapors as they pass u tirouch the tower, the fractionshaving'su stantially the samecompostion as' the circulated hydrocarbons and refluxin apart .of the excess separated condensed iydrocarbons noty used in circulation back to the still from which the mixed oil vapors were obtained and the remaining part of the excess separated condensed hydrocarbons back to, a successive still where a higher temperature is mainitained than in the still from which the vapors were obtained.

3. The rocess of fractionallyv separating mixed hy r'oearbons having. different boiling points which consists in vaporizing the hydrocarbons and passing them to the bottom of a fractionating tower and allowing them to rise through the tower to condense some of the vapors, circulating from an outlet near the bottom ofthe ractionating tower through -the'v upper part of said tower, li uid hydrocarbons condensed therein and ringing them into intimate contact `with the mixed oil vapors passing through said tower, thus separating from the vapors the fractions having substantially the same composition as the circulated hydrocarbons and reiuxing some of the resultant excess separated and condensed hydrocarbons not used in circulation back to the still from which the mixed oil vapors were obtained, passing some of the condensed hydrocarbons Vto a furthenfractionation by the Asame process in a second fractionating apparatus operated ata different temperature and separating and condensing the residual vapors from both `a paratuses.

4. The process o 'fractionally sepa-rating hydrocarbons having different boiling points,

which consistsin vaporizing the hydrocarbons and passing them to the bottom of a fractionating tower and allowin them to rise through the tower, circulating roman outlet near the bottom of the fractionating tower through the upper part of said tower liquid hydrocarbons condensed therein and bringing them into intimatecontact with the mixed `hydrocarbon oilvapors passing through said'.

tower, thusseparating from the vapors the fractions havingsubstantlally the same com- Aposition as the circulated hydrocarbons, re-

uxing some of the resultant excess se arated and condensed hydrocarbons not use in cir culation back to the still from which the mixed hydrocarbon oil vapors were obtalned, passing some of the condensed hydrocarbons to a further fractionation by the same process in a second ractionating apparatus operated at a different temperature and separatel pcondensing the residualvapors from bot apparatuses, then removing from both apparatuses the resultant excess separated and condensed hydrocarbons not used in circulation.- '70 5. The .process of fractionally separating mixed hydrocarboiis of;i different boiling points which consists` in vaporizing the hydrocarbons and passing them to the bottom of a fractionating tower, to condense the higher boiling'point fractions as the hvapors rise through the tower,' withdrawing from an arated and condensed hydrocarbons from the still and separately condensing the vapors finally issued from both stills.

6. The process ofI fractionating mixed hydrocarbons which are normally liquefied at atmospheric temperature, but 'have different boiling points, comprisinvr vaporizing the lmore volatile fractions and passing them to tlebot'tom of a fractionating tower .and allowing them to rise therethrough, leaving the residual liquid fractions in the still for subsequent disposal,"condensing some of the higher boiling point portions of said hydrocarbon vapors as they rise in the tower and cir'culatingva portion of the condensed hydrocarbonI vapors withdrawn from the bottompof'the tower througha cooler back to the -top of the tower and bringing this cooled condensate into intimatel contact with the rlsmg vapors,4s1multaneously regulating the temperature of `said .circulating liquid condensate by regulating the amount of condensate supplied tothe tower, and Aconducting the excess of the withdrawn condensate,

not remaining in circulation, back to the still from which it came. 7

7. The process of drocarbons which are normally liquefied at atmosphericv temperature, but have dierent boiling points, comprisin vaporizing the Imore volatile fractions an passing them to.

thev bottom ofa fractionating tower and allowing them to rise therethrough, leaving the residual liquid fractions in the still for subsequent disposal, condensing some-of the higher boiling point portions of said hydrocarbon vapors as they rise in the tower and circulating a portion of the'condensed hydrocarbon vapors withdrawn from the bot-y fractionating' mixed hytom of the tower through a cooler back to the top of the tower and bringing this cooled condensate into intimate 'contact with the rising vapors, simultaneously regulating the temperature of Lsaid circulating liquid coniso densate by regulating the amount of conthan in the still, from which the vapors were densate supplied to the tower, conducting a obtained. part of the excess of the Withdrawn con- In' testimony whereof we hereunto afx 10 densate, not remaining in circulation back to our signatures.

5 the still from which it came and the remaining part of the excess back to a successive still, i JOHN C. BLACK. Where a higher temperature is maintained` JAMES `W. `WEIR. 

